1. Field of the Invention
The present invention relates to ethylenically unsaturated, phosphorus-containing, bidentate ligands (monomers) and polymeric derivatives thereof as well as polymeric precursors to said polymeric derivatives and methods of making the same. The present invention also relates to catalyst compositions involving a Group VIII metal in the presence of the polymeric bidentate ligands and use of such catalysts in hydrocyanation, isomerization, and hydroformylation reactions.
2. Description of the Related Art
Phosphorus-based ligands are generally known in catalysis, finding use for a number of commercially important chemical transformations. Phosphorus-based ligands commonly encountered in catalysis include phosphines, phosphinites, phosphonites and phosphites. Monodentate phosphorus ligands, e.g. monophosphine and monophosphite ligands, are compounds that usually contain a single phosphorus atom that serves as an electron donor to a transition metal. Bidentate phosphorus ligands, e.g. bisphosphine, bisphosphinite, bisphosphonite, bisphosphite, and bis(phosphorus) ligands, in general, contain two phosphorus electron donor atoms and typically form cyclic chelate structures with transition metals.
Two particularly important industrial processes using phosphorus ligands as catalysts are olefin hydrocyanation and isomerization of branched nitriles to linear nitriles. Phosphite and phosphinite ligands are particularly good ligands for both reactions. The hydrocyanation of ethylenically unsaturated compounds (olefins) using transition metal complexes with monodentate phosphite ligands is well documented in the prior art. See, for example, U.S. Pat. Nos. 3,496,215; 3,631,191; 3,655,723; 3,766,237 and 5,543,536. Bidentate phosphite ligands have also been shown to be particularly useful ligands in the hydrocyanation of activated ethylenically unsaturated compounds. See, for example, J. Chem. Soc., Chem. Commun., 1991, 1292; J.Chem. Soc., Chem. Commun., 1991, 803; PCT Pat. App. WO 9303839; U.S. Pat. Nos. 5,512,696; 5,723,641; and 5,688,986. Bidentate phosphinite and phosphonite ligands are described in U.S. Pat. Nos. 5,817,850; 5,523,453; 5,693,843; and PCT Pat. App. WO 9964155, WO 9913983, WO 9946044, and WO 9843935.
Hydroformylation is another industrially useful process that utilizes catalysts made from phosphorus-containing ligands. The use of phosphine ligands, including diphosphines, is known for this purpose. The use of catalysts made from phosphite ligands is also known. Such catalysts usually contain a Group VIII metal, as described in, for example, U.S. Pat. No. 5,235,113.
Recovery of the ligand and catalyst is important for a successful commercial process. Typical separation procedures to remove the product(s) from the catalyst and ligand involve extraction with an immiscible solvent or distillation. It is usually difficult to recover the catalyst and ligand quantitatively. For instance, distillation of a volatile product from a non-volatile catalyst results in thermal degradation of the catalyst. Similarly, extraction results in some loss of catalyst into the product phase. For extraction, one would like to be able to select and/or control the solubility of the ligand and catalyst to disfavor solubility in the product phase. These ligands and metals are often very expensive and thus it is important to keep such losses to a minimum for a commercially viable process.
One method to solve the problem of catalyst and product separation is to attach the catalyst to an insoluble support. Examples of this approach have been previously described, and general references on this subject can be found in xe2x80x9cSupported Metal Complexes: A New Generation of Catalystsxe2x80x9d, F. R. Hartley and D. Boston, Reidel Publishing, 1985; Acta Polymer., 1996, 47, 1; xe2x80x9cComprehensive Organometallic Chemistryxe2x80x9d, Ed: G. Wilkinson, F. G. A. Stone, and E. W. Abel, New York: Pergamon Press, 1982, Chapter 55, xe2x80x9cPolymer Supported Catalystsxe2x80x9d; J. Mol. Catal. A, 1995, 104, 17; and Macromol. Symp., 1994, 80, 241. Specifically, monophosphine and monophosphite ligands attached to solid supports are described in these references. Bisphosphine ligands have also been attached to solid supports and used for catalysis, as described in, for example, U.S. Pat. Nos. 5,432,289 and 5,990,318; J. Mol. Catal. A, 1996, 112, 217, J.Chem. Soc., Chem. Commun., 1996, 653; J. Org. Chem., 1998, 63, 3137; Spec. Chem., 1998, 18, 224 and PCT Pat. App. WO 9812202. PCT Pat. Apps. WO 9906146 and WO 9962855 show use of supported phosphorus ligands in hydrocyanation and hydroformylation reactions, respectively. Bisphosphite ligands have also been grafted to solid supports such as those described in U.S. Pat. No. 6,121,184. The solid support in these prior art examples can be organic, e.g., a polymer resin, or inorganic in nature.
Polymer-supported multidentate phosphorus ligands may be prepared by a variety of methods known in the art, as described in U.S. Pat. Nos. 4,769,498 and 4,668,651, PCT Pat. App. WO 9303839 and WO 9906146, and European Pat. Apps. EP 0864577 A2 and EP 0877029 A2. The prior art discloses side-chain polymers containing multidentate phosphorus ligands as pendant groups.
Another method to solve the problem of separating the catalyst from the reaction product is to copolymerize phosphorus-containing ligands with other non-ligand monomers to produce insoluble phosphorus-containing ligands. Examples of such polymer-immobilized phosphine ligands have been reported in J. Am. Chem. Soc., 2000, 122, 6217 and J. Org. Chem., 1986, 51, 4189. In addition, polymer-immobilized phosphine-phosphite ligands and their use in hydroformylation catalysis have recently been described in Bull. Chem. Soc. Jpn., 1999, 72, 1911; J. Am. Chem. Soc., 1998, 120, 4051; and European Pat. App. EP 0864577.
To address the important issue of ligand recovery, this invention provides novel monomeric bidentate ligands and a method for their synthesis, polymeric bidentate ligands prepared from the monomeric ligands and a method for their synthesis, monomeric or polymeric phosphorus-containing compositions that may be combined with a Group VIII metal, and the use of this monomeric or polymeric phosphorus-containing composition combined with a Group VIII metal to act as a catalyst in reactions for hydrocyanation, hydroformylation, and isomerization. The polymeric, phosporus-containing catalyst composition is readily recoverable from the reaction products.
In its first aspect, the present invention provides novel, phosphorus-containing bidentate ligand (monomer) compounds as shown in Formula I or as shown in Formula II, substituted with a vinyl group and/or an acrylate group [e.g. ethenyl (CH2xe2x95x90CHxe2x80x94), propenyl ((CH3)(H)Cxe2x95x90CHxe2x80x94), acryloyl (CH2xe2x95x90CHxe2x80x94C(O)xe2x80x94Oxe2x80x94), or methacryloyl (CH2xe2x95x90C(CH3)xe2x80x94C(O)xe2x80x94Oxe2x80x94)]: 
wherein:
x=0 to 4;
y=0 to 2;
a and b individually are either 0, 1, or 2, provided a+b=2;
each Ar is individually phenyl or naphthyl, and the two Ar groups that are directly or indirectly (through an oxygen) bonded to the same phosphorus atom may be linked to each other by a linking unit selected from the group consisting of direct bond, alkylidene, secondary or tertiary amine, oxygen, sulfide, sulfone, and sulfoxide;
each R is individually hydrogen, ethenyl, propenyl, acryloyl, methacryloyl, an organic radical with a terminal ethenyl, propenyl, acryloyl, or methacryloyl group, linear or branched alkyl, cycloalkyl, acetal, ketal, aryl, alkoxy, cycloalkoxy, aryloxy, formyl, ester, fluorine, chlorine, bromine, perhaloalkyl, hydrocarbylsulfinyl, hydrocarbylsulfonyl, hydrocarbylcarbonyl or cyclic ether;
each Ar can be further substituted with linear or branched alkyl, cycloalkyl, acetal, ketal, aryl, alkoxy, cycloalkoxy, aryloxy, formyl, ester, fluorine, chlorine, bromine, perhaloalkyl, hydrocarbylsulfinyl, hydrocarbylsulfonyl, hydrocarbylcarbonyl or cyclic ether;
each Rxe2x80x3 is individually hydrogen, ethenyl, propenyl, an organic radical with a terminal ethenyl or propenyl group, linear or branched alkyl, cycloalkyl, acetal, ketal, aryl, alkoxy, cycloalkoxy, aryloxy, formyl, ester, fluorine, chlorine, bromine, perhaloalkyl, hydrocarbylsulfinyl, hydrocarbylsulfonyl, hydrocarbylcarbonyl or cyclic ether;
provided at least one R represents ethenyl, propenyl, acryloyl, methacryloyl or the organic radical with a terminal ethenyl, propenyl, acryloyl, or methacryloyl group or at least one Rxe2x80x3 represents ethenyl, propenyl, or the organic radical with a terminal ethenyl or propenyl group.
Preferred are compounds of Formula I wherein a=2, b=0, R is primary or secondary alkyl located ortho to the oxygen bonded to Ar, wherein yxe2x89xa71, and wherein at least one Rxe2x80x3 is primary or secondary alkyl group and is located at the ortho position of the oxygen bonded to the binaphthalene group, or a compound of Formula II wherein a=2, b=0, R is primary or secondary alkyl located ortho to the oxygen bonded to Ar, wherein xxe2x89xa71 and wherein at least one Rxe2x80x3 is primary or secondary alkyl group and is located at the ortho positions of the oxygen bonded to the biphenylene group.
In its second aspect, the invention is a process for preparing certain phosphorus-containing bidentate ligand (monomer) compounds of Formula I, wherein a is 1 or 2 and b is 0 or 1 with the condition that a+b=2, or certain compounds of Formula II, wherein a is 1 or 2 and b is 0 or 1 with the condition that a+b=2. The process comprises:
(1) reacting at least one of acryloyl chloride or methacryloyl chloride with a polyhydric alcohol to make at least one of monoacrylate or monomethacrylate,
(2) reacting at least one of the monoacrylate or monomethacrylate with at least one of phosphorus trichloride or phosphorodichloridite or aryldichlorophosphine (Cl2Pxe2x80x94Ar) to give at least one of phosphorochloridite- or aryl,aryloxychlorophosphinite-containing acrylate or methacrylate,
(3) reacting at least one of the phosphorochloridite- or aryl,aryloxychlorophosphinite-containing acrylate and/or methacrylate from step (2) with at least one compound of Formula III and/or at least one compound of Formula IV, 
wherein:
x=0 to 4;
y=0 to 2;
each Rxe2x80x2 individually is hydrogen or M, wherein M is an alkali metal or an alkaline earth metal,
each Rxe2x80x3 is individually hydrogen, ethenyl, propenyl, an organic radical with a terminal ethenyl or propenyl group, linear or branched alkyl, cycloalkyl, acetal, ketal, aryl, alkoxy, cycloalkoxy, aryloxy, formyl, ester, fluorine, chlorine, bromine, perhaloalkyl, hydrocarbylsulfinyl, hydrocarbylsulfonyl, hydrocarbylcarbonyl or cyclic ether.
Preferred are compounds of Formula III wherein a=2, b=0, R is primary or secondary alkyl located ortho to the oxygen bonded to Ar, wherein yxe2x89xa71, and wherein at least one Rxe2x80x3 is primary or secondary alkyl group and is located at the ortho position of the oxygen bonded to the binaphthalene group, or a compound of Formula IV wherein a=2, b=0, R is primary or secondary alkyl located ortho to the oxygen bonded to Ar, wherein xxe2x89xa71 and wherein at least one Rxe2x80x3 is primary or secondary alkyl group and is located at the ortho positions of the oxygen bonded to the biphenylene group.
In its third aspect, the present invention provides a method for making a polymeric, phosphorus-containing composition by heating, in the presence of an initiator, preferably a free radical initiator, and optionally in the presence of a Group VIII metal, a composition comprising at least one compound of Formula I and/or at least one compound of Formula II, provided at least one R represents ethenyl, propenyl, acryloyl, methacryloyl or the organic radical with a terminal ethenyl, propenyl, acryloyl, or methacryloyl group or at least one Rxe2x80x3 represents ethenyl, propenyl, or the organic radical with a terminal ethenyl or propenyl group.
In its fourth aspect, the present invention also provides a polymeric, phosphorus-containing composition made as described above in aspect three.
In its fifth aspect, the present invention also provides a method for producing a polymeric phosphorus-containing composition made by:
(1) heating in the presence of an initiator a composition comprising at least one compound of Formula III and/or at least one compound of Formula IV, 
wherein:
x=0 to 4;
y=0 to 2;
each Rxe2x80x2 individually is hydrogen, an alkali metal, an alkaline earth metal or a hydroxyl-protective group selected from alkyl, alkoxyalkyl (e.g., CH3OCH2xe2x80x94), carbonylalkyl (e.g., CH3xe2x80x94C(O)xe2x80x94), and a crown ether formed by taking both Rxe2x80x2 groups together;
each Rxe2x80x3 is individually hydrogen, ethenyl, propenyl, an organic radical with a terminal ethenyl or propenyl group, linear or branched alkyl, cycloalkyl, acetal, ketal, aryl, alkoxy, cycloalkoxy, aryloxy, formyl, ester, fluorine, chlorine, bromine, perhaloalkyl, hydrocarbylsulfinyl, hydrocarbylsulfonyl, hydrocarbylcarbonyl or cyclic ether;
provided at least one Rxe2x80x3 represents ethenyl, propenyl, or the organic radical with a terminal ethenyl or propenyl group;
by contacting the composition with an initiator, preferably a free radical initiator, and heating to a preselected temperature for a period of time sufficient to permit reaction, and
(2) phosphonylating the resulting polymer.
Preferred are compounds of Formula III wherein a=2, b=0, R is primary or secondary alkyl located ortho to the oxygen bonded to Ar, wherein yxe2x89xa71, and wherein at least one Rxe2x80x3 is primary or secondary alkyl group and is located at the ortho position of the oxygen bonded to the binaphthalene group, or a compound of Formula IV wherein a=2, b=0, R is primary or secondary alkyl located ortho to the oxygen bonded to Ar, wherein xxe2x89xa71 and wherein at least one Rxe2x80x3 is primary or secondary alkyl group and is located at the ortho positions of the oxygen bonded to the biphenylene group.
In its sixth aspect, the present invention further provides a polymer composition made as described above in aspect five.
In its seventh aspect, the present invention further provides a method to produce a polymeric, phosphorus-containing composition by heating a phosphorochloridite containing at least one acrylate or methyl acrylate group in the presence of an initiator, preferably a free radical initiator, to produce a polymer containing phosphorochloridite, and further reacting this polymer with at least one compound of Formula III and/or Formula IV wherein each Rxe2x80x2 individually is H or M, with the provision that if Rxe2x80x2 is protected, the protecting group must be removed before reacting the compound of Formula III and/or Formula IV with the polymer containing phosphorochloridite.
In its eighth aspect, the present invention further provides a polymer composition made as described above in aspect seven.
In its ninth aspect, the present invention further provides a catalyst composition comprising at least one monomeric, phosphorus-containing composition of aspect one and at least one Group VIII metal, and/or at least one polymeric, phosphorus-containing composition of aspect four and/or aspect six and/or aspect eight and at least one Group VIII metal, and/or at least one polymeric, phosphorus-containing, catalyst material of aspect three wherein the polymerization was carried out in the presence of at least one Group VIII metal.
In its tenth aspect, the present invention further provides the use of any of the present catalyst compositions for a hydrocyanation process comprising reacting an unsaturated organic compound with HCN in the presence of the catalyst composition, with or without a Lewis Acid.
In its eleventh aspect, the present invention further provides the use of any of the present catalyst compositions for an isomerization process comprising reacting an unsaturated organic nitrile compound in the presence of the catalyst composition.
In its twelfth aspect, the present invention further provides the use of any of the present catalyst compositions for a hydroformylation process comprising reacting an unsaturated organic compound with CO and H2 in the presence of the catalyst composition.